CN101357359A - Method for forming coating film - Google Patents

Method for forming coating film Download PDF

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Publication number
CN101357359A
CN101357359A CNA2008101301706A CN200810130170A CN101357359A CN 101357359 A CN101357359 A CN 101357359A CN A2008101301706 A CNA2008101301706 A CN A2008101301706A CN 200810130170 A CN200810130170 A CN 200810130170A CN 101357359 A CN101357359 A CN 101357359A
Authority
CN
China
Prior art keywords
coating
resin
film
noble metal
glittering material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2008101301706A
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Chinese (zh)
Inventor
今村毅
植村纯哉
高桥正志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paint Co Ltd
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Nippon Paint Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Publication of CN101357359A publication Critical patent/CN101357359A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • B05D5/068—Metallic effect achieved by multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B05D2601/02—Inorganic fillers used for pigmentation effect, e.g. metallic effect
    • B05D2601/10—Other metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/065—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y10T428/24868—Translucent outer layer
    • Y10T428/24876—Intermediate layer contains particulate material [e.g., pigment, etc.]

Abstract

The invention relates to a film forming method, comprising forming an undercoating film, a glittering material-containing base coating film and a clear coating film in this order on a substrate to be coated, in which a glittering material-containing base coating material for forming the glittering material-containing base coating film contains colloid particles containing a noble metal and/or a metal and a coating film-forming resin, and the undercoating film has a hue in a range of from +35 to +50 and -35 to -50 on a Munsell 100-hue ring with counterclockwise rotation on the hue ring being represented by from 0 to +50 and clockwise rotation being represented by from 0 to -50 where a hue of plasmon coloration of the colloid particles containing a noble metal and/or a metal is 0 on the hue ring, and has a brightness of 9 or less on a Munsell color system, or the undercoating film has an achromatic color having a brightness of 4 or less on a Munsell color system.

Description

The formation method of filming
Background of invention
1. invention field
The present invention relates to the formation method of multilayer film a kind of design performance excellence, that metallic luster is arranged.
2. correlation technique
In recent years, high design performance be body of a motor car, auto parts for example aluminium wheel, electronic product for example mobile phone is desired with the outward appearance of personal computer etc. and be important for giving these products with the same metallic luster of minute surface.As its a kind of technology, metal-plated embrane method and metal vapors sedimentation are known, and metallic luster gives this surface with this technology, so that a kind of outward appearance of design performance excellence to be provided.Yet the metal-plated embrane method has following shortcoming: the waste water that this method produced etc. brings very overall situation load, and the basic material of this method is confined to electric conductivity those.The metal vapors sedimentation has following shortcoming: basic material must place a vacuum chamber or pressure-reducing chamber, and this method can't be applied to the large foundation material.And then, in metal-plated embrane method and metal vapors sedimentation, all need main equipment, thereby also need a kind of alternative method from the cost viewpoint.
In these cases, development in recent years the technology of giving metallic luster by coating.For example, JP-A-11-343431 disclose a kind of contain by crushing metal steam deposited film for example the film formed metal fragment of aluminum vapor deposition as the coating of flitter, form a kind of method of filming with this coating of use, also disclose and to have utilized this coating to obtain a kind of filming of enough metallic luster that have.Yet this metallic luster of filming is strong unlike bright luster, thereby need a kind ofly can give the more formation technology of filming in high light pool from the position of design performance.
JP-A-2000-239853 discloses a kind of coating and the metallic film formation method of using this coating that contains the colloidal particles of noble metal or copper, has as the metallic luster of electroplating but also disclose this metallic film.Yet disclosed coating will satisfy required ability on the specific use among the JP-A-2000-239853, and still needs further improvement just can be used as general coating.Specifically, this coating is to be used to form circuit in the metallic film of electrode and electronic component etc., and JP-A-2000-239853 does not openly have for example formation of filming of bright luster of high design performance.
In order to form the multilayer film of metallic luster with design performance excellence, usually, be necessary to make and a kind ofly contain filming of glittering material and be configured as a kind of thin, even and continuous filming, and importantly develop a kind of suchlike coating of filming that is suitable for forming.The example of this coating comprises a kind of coating that contains the colloidal particles of noble metal etc., but is known that and uses these colloidal particles can cause other problem.Specifically, by be coated with this coating want on the substrates coated with nanometer scale arrange equably noble metal etc. colloidal particles, film by the thermosetting complete and continuous that adds subsequently then, be remarkable difficulty.Between the adjacent colloidal particles in this coating coating back, having under the situation in big gap, remaining unchanged in these colloidal particles filming after heating.As a result, plasmid gene group painted (plasmon coloration) occurs in the part that still has colloidal particles, this is owing to not providing desirable color to worsen design performance.
Brief summary of the invention
An object of the present invention is to provide a kind of formation method of filming with metallic luster of design performance excellence.
As for reaching the result that above-mentioned purpose of the present invention and other purpose are studied with keen determination, have been found that above-mentioned purpose and other purpose are to reach to form a kind of multilayer film that uses specific primer putty to film by the glittering material primer that contains of a kind of colloidal particles that contain noble metal and/or metal of coating on filming at a priming paint putty as pigment.
The present invention relates to a kind of by filming wanting to form a priming paint putty on the substrates coated in order; a bottom coating and the multilayer film formation method that varnish is filmed that contains glittering material; a kind of be used to form these colloidal particles that contain noble metal and/or metal and the tree film that becomes to film contain the luminescent material bottom coating contain the luminescent material primer; with on hue circle, be rotated counterclockwise on Munsell 100 hue circles that turn clockwise by 0～+ 50 expression by 0～-50 expression have+the priming paint putty of form and aspect in 35～+ 50 and-35～-50 scopes films; the painted form and aspect of plasmid gene group that wherein contain the colloidal particles of noble metal and/or metal are 0 on hue circle; and the briliancy on the Munsell color system be 9 or below, this priming paint putty achromatic colour of filming the briliancy on the Munsell color system be 4 or below.
According to the present invention, provide a kind of formation method of multilayer film of the metallic luster that the design performance excellence arranged.The bottom coating that contains glittering material in this multilayer film is a kind of thin, all even continuous filming, and the metallic luster of design performance excellence is arranged.This contains that the bottom coating of glittering material and specific primer putty are filmed and changes with suppressing the painted unfavorable form and aspect that cause of plasmid gene group, so that a kind of multilayer film that excellent design performance is arranged to be provided." the plasmid gene group is painted " this term of reference herein means the complementary color that the surperficial plasmid gene group by these colloidal particles occurs the absorption of the light of specific wavelength.Specifically, in the resulting multilayer film of the present invention, this priming paint putty form and aspect that surperficial plasmid gene group with these colloidal particles is absorbed of filming, thereby obtain the excellent design property energy." metallic luster is arranged " this term of mentioning herein means the intrinsic gloss of this noble metal when using noble metal as colloidal particles, and means the intrinsic gloss of this metal when using this metal as colloidal particles.
Better embodiment is described
In multilayer film formation method of the present invention, it is by using a kind of specific glittering material primer that contains to form in proper order by this on the substrates coated wanting that the bottom coating that priming paint putty films, contains glittering material and varnish are filmed.
[primer that contains glittering material]
The primer that contains glittering material that uses among the present invention contains and contains noble metal and/or metal (in this article a kind of belonging to, in some cases, can abbreviate " noble metal etc. " as) the glittering material of colloidal particles as pigment, and further contain a kind of one-tenth and be coated with film resin.This solids content that contains primer when coating of glittering material better is 1～5 (quality) %, be more preferably 1.2～4 (quality) %.Be lower than in this solids content under the situation of 1 (quality) %, may do not form a kind of continuous filming, and surpass under the situation of 5 (quality) % in this solids content, these colloidal particles may not be the form of microscopic particulates.The concentration (PWC) that contains the colloidal particles of noble metal etc. in the solids content when the coating of this coating better is 80～98 (quality) %, be more preferably 85～98 (quality) %.Be lower than in this concentration under the situation of 80 (quality) %, may can not get metallic luster, and surpass under the situation of 98 (quality) %, be used to form the lazy weight of this resinous principle of filming, and be difficult to form a kind of even, continuous filming in this concentration.The composition of the solids content of this coating except that the colloidal particles that contain noble metal etc. can suitably be determined because of purpose is different, and be benchmark with the solids content of the colloidal particles that contain noble metal etc., the content that this one-tenth is coated with film resin better is 1～15 (quality) %, be more preferably 5～15 (quality) %.Content at this resin is lower than under the situation of 1 (quality) %, may not form a kind of continuous filming, and surpass under the situation of 15 (quality) % at the content of this resin, may can not get filming of a kind of metallic luster that the design performance excellence arranged.
The primer that contains glittering material that uses among the present invention obtains with above-mentioned specific composition, and wherein the solids content in this coating the time is significantly little in coating, and this solids content major part is the colloidal particles as the noble metal of pigment etc.In the present invention, reduction and the high concentration colloidal particles (PWC) as solids content in the use of the colloidal particles of pigment, this coating provide a kind of filming of excellent metallic luster that have.
The colloidal particles that contain noble metal and/or metal in the primer that contains glittering material that uses among the present invention mean particle dia of 1～100nm of having an appointment, and these colloidal particles can for example liquid phase method and vapor phase method obtain with known method.For example, in a solution, these colloidal particles are to obtain with the generation step of colloidal particles that noble metal etc. is provided with to the concentration step that the colloidal particles solution of the resulting noble metal of this generation step etc. carries out ultrafiltration with a compound reduction that makes noble metal or metal in the presence of polymer pigment dispersant.The mean particle dia of these colloidal particles is to use the dynamic light scattering determination of laser and represent with median diameter by volume with a kind of.
The noble metal that uses in the primer that contains glittering material that uses among the present invention is not particularly limited, and the example comprises gold, silver, ruthenium, rhodium, palladium, osmium, iridium and platinum.In the middle of these, gold, silver, platinum and palladium are preferably, and silver and gold are because its high gloss is good especially.
The metal that uses in the primer that contains glittering material that uses among the present invention is not particularly limited, and the example comprises copper, nickel, bismuth, indium, cobalt, zinc, tungsten, chromium, iron, molybdenum, tantalum, manganese, tin and titanium.
The colloidal particles that contain noble metal and/or metal that use among the present invention can contain in above-mentioned noble metal and the metal at least 2 kinds with the form of composite (composition metal colloid) or with the form of simple mixtures (colloid mixture).The example of composition metal colloid includes the composition metal colloidal particles of core/shell structure.The composition metal colloid of mentioning herein mean contain multiple colloidal particles-wherein each all by two or more metals constitute-colloid, and the colloid mixture of mentioning herein means by mixing the colloid that two or more colloids obtain.
The compound of noble metal etc. that is used to prepare the colloidal particles of noble metal etc. is not particularly limited, as long as it contains this noble metal etc., the example comprises tetrahydro tetrachloro gold (III) acid (gold chloride), silver nitrate, silver acetate, crosses silver chlorate (IV), six hydration chlordene platinum (IV) (chloroplatinic acid), potassium chloroplatinate, Copper dichloride dihydrate (II), a hydrated copper acetate (II), copper sulphate (II), two hydration palladium bichlorides (II) and three rhodium trichloride hydrates (III).These can use separately, or wherein two or more are used in combination.
In the preparation method of the above colloidal particles, the compound of this noble metal etc. better uses in such a way, made before carrying out ultrafiltration the molar concentration in this solution such as this noble metal be 0.01mol/L or more than.Under the situation of this concentration＜0.01mol/L, the molar concentration of this noble metal etc. is too low and the efficient of deterioration is provided in the colloidal particles solution of resulting noble metal etc.From the viewpoint of efficient, this concentration be more preferably 0.05mol/L, further be more preferably 0.1mol/L or more than.
This polymer pigment dispersant is a kind ofly to contain with the high functional group of the affinity of these colloidal particles and solvent is had high molecular weight copolymer part, that have amphotericity of affinity, and the pigment dispersing agent when being commonly used to produce as pigment paste.
In the preparation method of these colloidal particles, this polymer pigment dispersant is that the colloidal particles with noble metal etc. exist, and considers that this polymer pigment dispersant stablized the dispersity of colloidal particles in this solvent of this noble metal etc.The number-average molecular weight of this polymer pigment dispersant better is 1,000～1,000,000.Under the situation of this number-average molecular weight＜1,000, make the stable function possibility of this dispersity not enough, and surpass under 1,000,000 the situation at it, this dispersant may be difficult to operation owing to high viscosity.From these viewpoints, this number-average molecular weight is more preferably 2,000～500, and 000, further be more preferably 4,000～500,000.This number-average molecular weight is to be obtained by gel permeation chromatography (GPC) method based on polystyrene standard.
This polymer pigment dispersant is not particularly limited, as long as satisfy above-mentioned performance, the example comprises those disclosed among the JP-A-11-80647.Therefore, can use the commercially available prod, the example comprises Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse32550, Solsperse 35100, Solsperse 37500 and Solsperse 41090 (all producing) by Lubrizol company, Disperbyk 160, Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, and Disperbyk 182, and Disperbyk 183, Disperbyk 184, Disperbyk 190, and Disperbyk 191, and Disperbyk 192, Disperbyk 2000 and Disperbyk 2001 (all producing) by BYK ChemieGmbH, Polymer 100, and Polymer 120, and Polymer 150, Polymer 400, Polymer 401, and Polymer 402, and Polymer 403, Polymer450, Polymer 451, and Polymer 452, and Polymer 453, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-1501, EFKA-1502, EFKA-4540 and EFKA-4550 (all producing), FlowlenDOPA-158 by EFKA Additives company, Flowlen DOPA-22, Flowlen DOPA-17, Flowlen G-700, Flowlen TG-720W, Flowlen 730W, Flowlen 740W and Flowlen 745W (all producing) by Kyoeisha chemical company, Adisper PA111, Adisper PB711, Adisper PB811, Adisper PB812 and Adisper PW911 (all producing) and Joncryl 678 by Ajinomoto company, Joncryl 679 and Joncryl 62 (all producing) by JohnsonPolymer company.These can use separately, also can be with being used in combination of two or more wherein.
Total amount with this noble metal etc. in the compound of noble metal etc. and this polymer pigment dispersant is a benchmark, and the use amount of this polymer pigment dispersant better is 30 (quality) %.Under this quantity surpassed the situation of 30 (quality) %, the concentration of the noble metal of solids content etc. possibly can't be brought up to the purpose level in this solution, although this solution carries out ultrafiltration in concentration step after a while.From these viewpoints, total amount with this noble metal etc. in the compound of noble metal etc. and this polymer pigment dispersant is a benchmark, the use amount of this polymer pigment dispersant be more preferably 20 (quality) % or following, further be more preferably 10 (quality) % or following.
In the preparation method of these colloidal particles, during reduction such as the compound of noble metal etc., better use amine as reducing agent.For example, a kind of amine is added in the solution of the compound of noble metal etc. and polymer pigment dispersant, this solution is mixed, stirs, thereby make this precious metal ion or metal ion about room temperature, be reduced into noble metal or metal.The use of amine make noble metal etc. compound also proper energy about 5～100 ℃, better 20～80 ℃ reaction temperature is carried out and need not the high and harmful reducing agent of application risk, also need not to use heating or special light radiation appliance.
This amine is not particularly limited, and can use those disclosed among the JP-A-11-80647.The example comprises aliphatic amine, for example propylamine, butylamine, hexylamine, diethylamine, di-n-propylamine, dimethyl amine, diethyl methylamine, triethylamine, ethylenediamine, N, N, N ', N '-tetramethylethylenediamine, 1,3-diaminopropanes, N, N, N ', N '-tetramethyl-1,3-diaminopropanes, trien and tetren; Cycloaliphatic amines, for example piperidines, N-methyl piperidine, piperazine, N, N '-lupetazin, pyrrolidines, N-crassitude and morpholine; Aromatic amine, for example aniline, methylphenylamine, N, accelerine, toluidines, anisidine and phenetidine; And aralkylamine, for example benzylamine, N-methylbenzylamine, N, N-dimethyl benzylamine, phenyl ethylamine, benzene dimethylamine and N, N, N ', N '-durol dimethylamine.The example of this amine also comprises alkanolamine, for example methyl aminoethanol, dimethylamino-ethanol, triethanolamine, monoethanolamine, diethanol amine, methyl diethanolamine, Propanolamine, 2-(the amino Propylamino of 3-) ethanol, butanolamine, hexanol amine and dimethylamino propyl alcohol.These can use separately, also can be with being used in combination of two or more wherein.In the middle of these, hydramine is preferably, and dimethylamino-ethanol is better.
The example of the reducing agent except that amine comprises alkali metal borohydride for example sodium borohydride, hydrazine compound, azanol, citric acid, tartaric acid, ascorbic acid, formic acid, formaldehyde, dithionite and sulfoxylate derivative.In the middle of these, citric acid, tartaric acid and ascorbic acid are preferably, because they obtain easily.These can use separately, also can be used in combination with this amine, and under the situation that this amine and citric acid, tartaric acid or ascorbic acid are used in combination, citric acid, tartaric acid or ascorbic acid better use with the form of salt.Citric acid and sulfoxylate derivative can be by using with iron (II) ion population and improving aspect its reducing power.
The addition of this reproducibility compound better is the such quantity of the necessary quantity of reduction such as noble metal that are equal to or greater than in the compound that makes noble metal etc.Quantity at this reproducibility compound is lower than under the situation of this necessary amounts, and this reduction may be carried out insufficiently.The upper limit of this addition is not particularly limited, but it better be make 30 times of necessary quantity of reduction such as noble metal in the compound of noble metal etc. following, better 10 times or below.Except that the chemical reduction method that is undertaken by interpolation reproducibility compound, also can adopt a kind of radiant light reducing process of using high-pressure sodium lamp.
The adding method of this reproducibility compound is not particularly limited, and for example, this reproducibility compound can add after adding this polymer pigment dispersant.In this case, this polymer pigment dispersant is dissolved in a kind of solvent, and one of compound of this reproducibility compound and this noble metal etc. further is dissolved in wherein forms a kind of solution, wherein add another kind in the compound of this reproducibility compound and this noble metal etc. to reduce.As another example of the method for adding this reproducibility compound, this polymer pigment dispersant and this reproducibility compound are mixed in advance, and this mixture is added in a kind of solution of compound of this noble metal etc.
The colloidal particles solution of noble metal that is obtained like this by reduction step etc. carries out ultrafiltration, so that a kind of colloidal particles solution that high concentration and small amount of impurities (for example other various ions, salt, amine and polymer pigment dispersant) is arranged and be suitable for preparing the primer that contains glittering material to be provided.The content that carries out this noble metal in the solids content of the solution after this processing or metal better is 83～99 (quality) %, be more preferably 90～98 (quality) %, further be more preferably 93～98 (quality) %.Be under the situation of formulations prepared from solutions of content＜83 (quality) % by using a kind of this noble metal or metal at this primer that contains glittering material, under the situation of this medium heating condition when forming of filming, glossiness may go wrong.Content at this noble metal etc. surpasses under the situation of 99 (quality) %, and the dispersion stabilization of these colloidal particles may be undermined.
In the colloidal particles solution that obtains in the above described manner in the contained solids content content of this noble metal or this metal greater than resulting with usual way.Therefore, the use that contains the primer that contains glittering material of these colloidal particles can provide a kind of to have high gloss and filming of metal appearance and not to have the metal particle outward appearance, film as electroplating sample, even as the same when compare heating condition when filming formation with common mode be medium.Therefore, for example can form filming of a kind of metal appearance that high gloss and no metal particle outward appearance arranged on plastics and the paper, film as plating at the low relatively base material of heat resisting temperature.
The example that contained one-tenth is coated with film resin in the primer that contains glittering material that uses among the present invention comprises acrylic resin, mylar, alkyd resins, epoxy resin, polyurethane resin and polyether resin, these one-tenth are coated with film resin and can use separately, also can be with being used in combination of two or more wherein.This one-tenth is coated with those of those and lacquer type that film resin includes curing performance, and general those that curing property functional group is arranged that use.The resin that curing property functional group arranged by with a kind of crosslinking agent for example amino resins, (end-blocking) polyisocyanate compound, amines, polyamide compound, imidazolium compounds, imidazolinium compounds and polybasic carboxylic acid mixes use, and its curing reaction can be by heating or carrying out at normal temperature.The lacquer type of curing property functional group does not become to be coated with film resin and becoming to be coated with film resin and can being used in combination of curing property functional group is arranged.This crosslinking agent better is at least a in amino resins and the blocked polyisocyanates compound.Under the situation of using this crosslinking agent, the ratio that this one-tenth is coated with film resin and this crosslinking agent generally is that 99～50 (quality) % becomes to be coated with film resin and 1～50 (quality) % crosslinking agent, better is that 99～70 (quality) % becomes to be coated with film resin and 1～30 (quality) % crosslinking agent that these are all with solid content meter.Under the situation of ratio＜1 of this crosslinking agent (quality) % (promptly this one-tenth is coated with the ratio of film resin above 99 (quality) %), crosslinked can not fully the carrying out during this is filmed.On the other hand, surpass under the situation of 50 (quality) % (promptly this one-tenth is coated with ratio＜50 (quality) % of film resin) in the ratio of this crosslinking agent, the bin stability of this coating worsens and its curing rate improves to such an extent that this outward appearance of filming is worsened.
The example of acrylic resin comprises the copolymer of a kind of acrylic monomer and another kind of ethylene linkage unsaturated monomer.The example of operable acrylic monomer comprises acrylic acid and methacrylic acid and methyl in this copolymer, ethyl, propyl group, normal-butyl, isobutyl group, the tert-butyl group, the 2-ethylhexyl, lauryl, phenyl, benzyl, the 2-hydroxyethyl, the 2-hydroxypropyl, the ester compounds of 4-hydroxybutyl etc., the open loop adduct of caprolactone and acrylic or methacrylic acid 2-hydroxy methacrylate, glycidyl acrylate, GMA, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, (methyl) acrylate of polyalcohol, acrylic acid, methacrylic acid and described after a while phosphorous acidic group (methyl) acrylate.Can comprise styrene, AMS, itaconic acid, maleic acid and vinyl acetate with the example of the ethylene linkage unsaturated monomer of this acrylic monomer polymerization.
The example of mylar comprises saturated polyester resin and unsaturated polyester resin, especially comprises the condensation product that polyacid and polyalcohol obtain under heating.The example of polyacid comprises saturated polybasic acid for example phthalic anhydride, terephthalic acid (TPA) and butanedioic acid, and unsaturated polyacid for example maleic acid, maleic anhydride and fumaric acid.Examples of polyhydric alcohols comprises dihydroxylic alcohols for example ethylene glycol and diethylene glycol (DEG), and trihydroxylic alcohol glycerine and three (methylol) propane for example.
The example of alkyd resins comprises by polyacid and polyalcohol and a kind of modifier alkyd resins that obtains of fat or aliphatic acid (as soybean oil, linseed oil, coconut oil and stearic acid) reaction for example, and natural resin (for example rosin and amber).
The example of epoxy resin comprises the resin that is obtained by bis-phenol and chloropropylene oxide reaction.The example of this bis-phenol comprises bisphenol-A and Bisphenol F.The example of this bisphenol-type epoxy resin comprises Epikote 828, Epikote 1001, Epikote 1004, and Epikote 1007 and Epikote 1009 (all by shell chemical company produce) also can use by increase those that chain obtains with a kind of suitable cahin extension agent.
The example of polyurethane resin includes by making for example resin of the ammonia ester bond that obtains of acrylate, polyester, polyethers and Merlon and a kind of polyisocyanate compound reaction of a kind of how pure composition.The example of polyisocyanate compound comprises 2,4-toluene di-isocyanate(TDI) (2,4-TDI), 2,6-toluene di-isocyanate(TDI) (2,6-TDI), its mixture (TDI), diphenyl-methane-4,4 '-vulcabond (4,4 '-MDI), diphenyl-methane-2,4 '-vulcabond (2,4 '-MDI), its mixture (MDI), naphthalene-1,5-vulcabond (NDI), 3,3 '-dimethyl-4,4 '-biphenyl diisocyanate, XDI (XDI), dicyclohexyl methyl hydride diisocyanate (hydrogenation HDI), IPDI (IPDI), hexamethylene diisocyanate (HDI) and hydrogenation of benzene dimethylene diisocyanate (HXDI).
The example that belongs to the polyether resin of polymer that ehter bond is arranged or copolymer comprises that each molecule has the polyether resin of at least 2 hydroxyls, for example polyoxyethylene polyethers, polyoxy propylidene polyethers, polyoxy butylidene polyethers and from aromatic polyhydroxy compounds bisphenol-A and the Bisphenol F polyethers of deriving for example.The example also comprises by what make that for example a kind of polybasic carboxylic acid of this polyether resin and a kind of reactive derivatives such as butanedioic acid, adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) and trimellitic acid and anhydride reactant thereof obtain and contains the carboxyl polyether resin.
The better example that this one-tenth is coated with film resin comprises acrylic resin and mylar, and acrylic resin is good especially, is further preferably and the acrylic resin (being designated hereinafter simply as phosphorous acidic group acrylic resin) of phosphate is arranged.The content that this one-tenth is coated with the solids content of phosphorous acidic group acrylic resin in the solids content of film resin better is 30～100 (quality) %, be more preferably 50～100 (quality) %.Under the situation of content＜30 (quality) % of the solids content of phosphorous acidic group acrylic resin, resistance to water and cohesive may be influenced.
The example of phosphorous acidic group acrylic resin comprises by making a kind of acrylic resin that is obtained by the monomer and the copolymerization of another kind of ethylene linkage unsaturated monomer of following general formula (I) representative:
X represents hydrogen atom or methyl in the formula; The Y representative has the alkylidene of 2～4 carbon atoms; And n represents 3～30 integer.
The monomer of general formula (I) representative can be such as synthetic in such a way: a kind of alkylene oxide is added on (methyl) acrylic acid by addition reaction, generate a kind of polyalkylene glycol mono ester, make itself and phosphoryl chloride phosphorus oxychloride reaction so that phosphoric acid esterification makes resulting product hydrolysis then then.This monomer can be synthetic with conventional method by using orthophosphoric acid, metaphosphoric acid, phosphoric anhydride, phosphorus trichloride, phosphorus pentachloride etc. to replace phosphoryl chloride phosphorus oxychloride.
In this addition reaction, the addition of this alkylene oxide can be a stoichiometric amount basically, promptly with general formula (I) in the corresponding n mol of n, and usually be 3～30mol, better 4～15mol, 5～10mol/mol (methyl) acrylic acid especially.The example of this alkylene oxide includes those of 2～4 carbon atoms.Its instantiation comprises oxirane, expoxy propane and epoxy butane.The example of the catalyst that uses in this reaction comprises potassium hydroxide and NaOH.The example of the solvent that uses in this reaction comprises the N-methyl pyrrolidone.Reaction temperature can be 40～200 ℃, and the reaction time can be on 0.5～5 the time.
After this addition reaction, carry out mono-esterification with phosphoryl chloride phosphorus oxychloride.This esterification can be according to conventional method, for example carry out time of 0.5～5 hour 0～100 ℃ temperature.The use amount of phosphoryl chloride phosphorus oxychloride can be a stoichiometric amount, for example 1～3mol/mol addition reaction product.
Then, resulting product is according to the conventional method hydrolysis, so that the monomer (i) of general formula (I) representative to be provided.The instantiation of monomer (i) comprises acid phosphorus oxygen base six (oxygen propylidene) monomethacrylates and acid phosphorus oxygen base 12 (oxygen propylidene) monomethacrylates.
Monomer (i) and another kind of ethylene linkage unsaturated monomer are (ii) used the conventional method copolymerization, so that this phosphorous acidic group acrylic resin to be provided.Ethylene linkage unsaturated monomer example (ii) is included as the synthetic described acrylic monomer and the ethylene linkage unsaturated monomer of acrylic resin.The example of this copolymerization process comprises a kind of like this method: monomer mixture is mixed with a kind of known polymerization initiator (for example azodiisobutyronitrile), and with this mixture be added drop-wise in a kind of solvent (for example propane diols list ethylether) that has been heated to polymerization temperature, aging subsequently.Though polymerizing condition can suitably be selected, for example this polymerization temperature can be that 80～150 ℃, polymerization time can be 1～8 hour.
In the composition of this polymerisation, for per 100 mass parts monomers (i), monomer quantity (ii) better is 200～5000 mass parts.Under the situation of monomer quantity＜200 mass parts (ii), resistance to water may worsen, and surpasses under the situation of 5000 mass parts in monomer quantity (ii), and the effect of this phosphate can't manifest sometimes.
The acrylic resin of this phosphorous acidic group better has: the acid number of phosphate is 70～150mgKOH/g, and the total acid number that comprises the acid number of other acidic group is 70～200mgKOH/g, and hydroxyl value is 50～220mgKOH/g, and number-average molecular weight is 2,000～8,000.
Under the situation of the acid number＜70mgKOH/g of the phosphate of the acrylic resin of this phosphorous acidic group, this bottom coating that contains glittering material may break, and resistance to water may further worsen.Surpass under the situation of 150mgKOH/g at it, this bin stability that contains the primer of glittering material may worsen.From these viewpoints, the acid number of this phosphate is 75～120mgKOH/g better.
Under the situation of the total acid number＜70mgKOH/g of acid number acrylic resin, that comprise other acidic group of this phosphorous acidic group, this bottom coating that contains glittering material may break, and resistance to water may further worsen.Surpass under the situation of 200mgKOH/g at it, this bin stability that contains the primer of glittering material may worsen.From these viewpoints, this total acid number is 75～150mgKOH/g better.
Under the situation of the hydroxyl value＜50mgKOH/g of the acrylic resin of this phosphorous acidic group, resistance to water may worsen, and surpasses under the situation of 220mgKOH/g at it, the possibility of result of Water Resistance Test since foaming worsen.From these viewpoints, this hydroxyl value is 70～180mgKOH/g better.
Under the situation of number-average molecular weight＜2000 of the acrylic resin of this phosphorous acidic group, this bottom coating that contains glittering material may break, and curing performance may worsen.Surpass under 8000 the situation at it, this outward appearance of filming may worsen, and the operability of this coating may be owing to high viscosity worsens.From these viewpoints, this number-average molecular weight is 3,000～6,000 better.
This primer that contains glittering material better contains the acrylic resin of this phosphorous acidic group with the quantity of 0.01～20 mass parts, better 0.1～15 mass parts, further better 0.2～13 mass parts for the solids content of per 100 these coating of mass parts.Under the too little situation of the content of the acrylic resin of this phosphorous acidic group, this bottom coating that contains glittering material may break.Under the too big situation of the content of the acrylic resin of this phosphorous acidic group, there is this outer light of filming to worsen such trend.
This contains the priming paint material of glittering material, except that mentioned component, a kind of lubricity dispersion liquid, the Tissuemat E that can also contain polyamide wax and be aliphatic amide is a kind of colloidal dispersion that mainly contains oxidic polyethylene, sagging inhibitor, curing catalysts, ultra-violet absorber, light stabilizer, antioxidant, equal for example silicone and organic polymers of paint, surface amendment, antidrip agent, thickener, defoamer, lubricant, the cross-linked polymer particles (microgel) etc. of dropping down all contain not damage the such quantity of advantage of the present invention.
This primer that contains glittering material can take various forms, and comprises solvent-borne type, aqua type, powder-type etc.In the middle of these, solvent based coating is preferably, because it is excellent forming thin aspect filming uniformly, the better example of its solvent comprises ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, propyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol isopropyl ether, ethylene glycol 2-ethyl hexyl ether, 3-methyl-3-methoxybutanol, the 3-methoxybutanol, ethylene glycol ether, ethylene glycol monobutyl ether, two glycerine monomethyl ethers, diethylene glycol monoethyl ether, acetate diethylene glycol monoethyl ether ester, propylene glycol monomethyl ether, and dihydroxypropane single-ether.Solvent based coating and aqua type coating can be one-component coating or two-component coating.
In the formation method of filming of the present invention, priming paint putty is filmed, is contained the bottom coating of glittering material and varnish and films and form on the substrates coated wanting with this order, and this primer that contains glittering material is to be used to form this bottom coating that contains glittering material.The coating of respectively filming can bump wet method with wetting or the wet dry method of bumping forms.The primer that contains glittering material that uses among the present invention contains this colloidal particles that contain noble metal etc., and the film coating of going up coating of this priming paint putty is painted owing to the plasmid gene group takes place the inhomogeneities on the nanometer level.Specifically, under the big situation of the distance between the adjacent colloidal particles in this coating coating back, these colloidal particles are still as they filming after heating, and painted in the part generation plasmid gene group that contains these colloidal particles.In the present invention; the unfavorable form and aspect that the use that specific primer putty is filmed has suppressed to cause owing to the plasmid gene group is painted change, thereby a kind of like this multilayer film that demonstrates intrinsic form and aspect such as contained this noble metal in these colloidal particles and gloss and excellent design performance is arranged is provided.
[wanting substrates coated]
Want substrates coated to be not particularly limited among the present invention, the example comprises metal for example iron, aluminium, copper and alloy thereof; Inorganic material is glass, cement and concrete for example; Plastic material is resin material such as polyvinyl resin, acrylic resin, ethylene-vinyl acetate copolymer resin, polyamide, acrylic resin, vinylidene resin, polycarbonate resin, polyurethane resin and epoxy resin for example, and various types of other FRP; With natural material and synthetic material, for example timber, paper and fibrous material such as cloth.Want the better example of substrates coated to comprise metal for example iron, aluminium, copper and alloy thereof, and method of the present invention can advantageously be applied to body of a motor car and for example coating of aluminium wheel of auto parts.
[priming paint putty is filmed]
In the present invention, priming paint putty is filmed and is formed on the substrates coated wanting.It is important in the present invention that this priming paint putty is filmed; and this contains appropriate combination that filming of glittering material film with this priming paint putty and uses and can suppress can also improve the glossiness of this multilayer film because these form and aspect that contain painted this multilayer film that causes of plasmid gene group of the colloidal particles that contain noble metal etc. in the filming of glittering material change.
Therefore; the priming paint putty that uses among the present invention is filmed and is equaled or approach the form and aspect that contained this in this coating that contains glittering material contains painted complementary color such as the plasmid gene group of colloidal particles of noble metal etc.; and have on the Munsell color system 9 or following briliancy, or have on the Munsell color system 4 or the achromatic colour of following briliancy.The form and aspect that equal or approach this complementary color can be expressed with the Munsell color system; and on Munsell 100 hue circles, be in+35～+ 50 and-35～-50 scope in; wherein being rotated counterclockwise by 0～+ 50 on this hue circle represented; and turn clockwise by 0～-50 representative, wherein these painted form and aspect of plasmid gene group that contain that contained this in the coating of glittering material contain the colloidal particles of noble metal etc. are 0 on this hue circle.
This priming paint putty film equal or approach the form and aspect of the painted complementary color of this plasmid gene group and have 9 or the situation of following briliancy under, owing to the form and aspect variation of painted this multilayer film that causes of this genome can be suppressed.This priming paint putty film briliancy be 4 or the situation of following achromatic colour under, owing to the painted form and aspect variation that causes of this plasmid gene group can be suppressed, and can obtain excellent glossiness.The plasmid gene group of mentioning herein painted (plasmoncoloration) means via the surperficial plasmid gene group (surface plasmon) of metal superfine particulate to the absorption of light that specific wavelength is arranged and the complementary color that occurs.
The painted instantiation of plasmid gene group that contains the colloidal particles of noble metal etc. comprises the yellow of silver colloid and the redness of gold colloid.Therefore, this priming paint putty form and aspect of filming better are that silver colloid is that purplish blue (PB) look or gold colloid are bluish-green (BG) look.Regardless of the kind of colloid, can use briliancy is 4 or following achromatic colour, promptly approaches the achromatic colour of black.
This priming paint putty is filmed, and the viewpoint from the design performance of this multilayer film has+form and aspect in 35～+ 50 and-35～-50 scopes and 9 or following briliancy.
In the present invention, the color that this priming paint putty is filmed is suitably to select, and is suppressed thereby the form and aspect that cause owing to the plasmid gene group of these colloidal particles is painted are changed, and the glossiness of this multilayer film is improved, and improve its design performance.The design performance of this multilayer film that obtains by the feature of utilizing this priming paint putty to film is improved, and what can form by the coating that contains glittering material with the colloidal particles that contain noble metal etc. with this contains the combination of glittering material bottom coating as thin as a wafer and advantageously obtain.Therefore, use the form and aspect that absorb via surperficial plasmid gene group by the metal superfine particulate form and aspect, just can obtain advantage of the present invention as this priming paint putty coating.
This priming paint putty is filmed and is not particularly limited, as long as it satisfies the condition relevant with form and aspect and briliancy and can form according to the known technology of priming paint putty material.For example, this priming paint putty film can be by solvent-borne type (organic solvent type or aqua type) coating spraying or electro-deposition is coated with or the spraying of powdery paints forms.
Wanting substrates coated is under the situation of body of a motor car or auto parts, substrates coated better to carry out ungrease treatment or chemical conversion in advance and handles, and better form the bottom coating that is made of electrodeposition coating.Wanting substrates coated is under the situation as the casting of auto parts or forged aluminium wheel, better forms the bottom coating that is made of transparent powder paint.
The build that the priming paint putty that uses among the present invention is filmed is different because of purpose, and can be in 5～100 μ m, better 7～80 mu m ranges.Under the situation of thickness＞100 μ m that this priming paint putty is filmed, definition may reduce, and this is filmed and inhomogeneities or progressive deformation may occur.Under the situation of this thickness＜5 μ m, hidden ability may become not enough and cause that this is coated with film rupture.
[bottom coating that contains glittering material]
In the present invention, the primer that this is contained glittering material is coated on this priming paint putty and films and go up, heat to form the bottom coating that this contains glittering material then.This coating process that contains the primer of glittering material is not particularly limited, and for example, this coating can use for example coatings such as flush coater, spin coater, roll coater, silk screen and ink-jet utensil, heavy automatic doubler surface glouer, electrophoresis equipment of coating apparatus.In the middle of these coating processes, spraying process is preferably, because it is excellent with regard to forming thin for filming uniformly.Heating means are not particularly limited, and for example, can use gas furnace, electric furnace, IR stove etc. as heating furnace.
This coating weight that contains the primer of glittering material can be looked purpose and at random be determined, because it is different because of the concentration of the colloidal particles of this noble metal etc., coating process etc.This build that contains the bottom coating of glittering material is not particularly limited, and usually is 0.01～1 μ m, better 0.02～0.3 μ m.
[varnish is filmed]
In the present invention, to film be to form on this contains the bottom coating of glittering material to varnish.In order to protect this bottom coating that contains glittering material, to film be necessary to this varnish of one deck at least.Be used for the varnish paint that this varnish films and be not particularly limited, the example comprises water white transparency coating, unglazed clear dope and complexion clear dope, and these can suitably be selected because of purpose is different.This clear dope can be used in combination, and films to be formed with 2 layers or more multi-layered varnish.
As this water white transparency coating, can use the water white transparency coating that usually is used as finish, for example, can use the mixture of thermosetting resin and crosslinking agent.This thermosetting resin can be selected from following at least a: acrylic resin, mylar, fluororesin, epoxy resin, polyurethane resin, polyether resin and modified resin thereof.Solvent based coating and water based paint also can use, and can be a kind of based one-pack-type coating or a kind of bi-component resin, for example bi-component ammonia ester resin paint.
This water white transparency coating in case of necessity, in the scope of not damaging its transparency, can contain additive for example modifier, ultra-violet absorber, levelling agent, dispersant and defoamer.
The dried film thickness that this water white transparency is filmed better is 10～80 μ m, exceeds at this dried film thickness under the situation of this scope, and this outward appearance of filming may be not enough.The thickness that this water white transparency is filmed is 20～50 μ m better.
This unglazed clear dope contains a kind of supporting agent and a kind of delustering agent.This supporting agent can be the supporting agent that usually is used as finish, and, for example, can use the mixture of thermosetting resin and crosslinking agent.This thermosetting resin can be selected from following at least a: acrylic resin, mylar, fluororesin, epoxy resin, polyurethane resin, polyether resin and modified resin thereof.
The dried film thickness of this unglazed transparent coating better is 10～50 μ m.Under the situation of this dried film thickness＜10 μ m, be difficult to obtain a kind of high-quality unglazed outward appearance, and it＞situation of 50 μ m under, this outward appearance of filming may worsen.The dried film thickness of this unglazed transparent coating is 20～40 μ m better.
The delustering agent that uses in this unglazed clear dope can be various delustering agents, and better is at least a in resin microscopic particulates or the inorganic microscopic particulates.The example of resin microscopic particulates comprises acrylic resin, polyacrylonitrile, polyurethane, polyamide and polyimides.The average particle diameter of this resin microscopic particulates better is 10～25 μ m.Under the situation of this average particle diameter＜10 μ m, high-quality delustring outward appearance may manifest insufficiently and a kind of too smooth texture is provided.Under the situation of this average particle diameter＞25 μ m, the surface of this unglazed transparent coating seems uneven and a kind of too coarse texture is provided.
The example of this inorganic microscopic particulates comprises silica fine powder, clay, talcum and mica.The average particle diameter of this inorganic microscopic particulates better is 1～5 μ m.Under the situation of this average particle diameter＜1 μ m, high-quality unglazed outward appearance may manifest insufficiently and a kind of too smooth texture is provided.Under the situation of average particle diameter＞5 μ m, the surface of this unglazed transparent coating seems uneven and a kind of too thick texture is provided.This resin microscopic particulates and this inorganic microscopic particulates can be used in combination.Its ratio better is 0.001～100 mass parts, this inorganic microscopic particulates of better 0.1～10 mass parts for this resin microscopic particulates of per 1 mass parts.
For design performance, effectively, in this unglazed clear dope, be used in combination some kinds of resin microscopic particulates and inorganic microscopic particulates.The content of this delustering agent is the solid content meter of benchmark according to the solids content with this coating, better is 10～60 (quality) %.Under the situation of this content＜10 (quality) %, can't obtain high-quality unglazed outward appearance, and it＞situation of 60 (quality) % under, this intensity of filming may be not enough.The content of this delustering agent with solid content meter, is 25～50 (quality) % better.
This unglazed clear dope can contain additive in case of necessity, for example coloring pigment, extender pigment, modifier, ultra-violet absorber, even paint, dispersant and defoamer.
This unglazed clear dope can be any in organic solvent type, aqua type, the powder-type.This organic solvent type and aqua type coating can be one-pack type or two-component-type, for example hypergolic polyurethane resin coating.The unglazed transparent coating that forms with this unglazed clear dope toasts one period scheduled time 120～160 ℃ temperature subsequently, films to finish this.
Colourful transparent coating contains a kind of supporting agent and a kind of coloring pigment.This supporting agent can be usually be used as finish the sort of, for example, can use the mixture of thermosetting resin and crosslinking agent.This thermosetting resin can be selected from following at least a: acrylic resin, mylar, fluororesin, epoxy resin, polyurethane resin, polyether resin and modified resin thereof.This colourful transparent coating can have all kinds, for example solvent-borne type, aqua type and powder-type.This solvent based coating and aqua type coating can be the one pack system type or bicomponent type resin, for example hypergolic polyurethane resin coating.
The example of the coloring pigment that uses in the colourful transparent coating comprises the azo lake pigment as organic pigment, soluble AZOpigments, condensed azo pigment, diketo-pyrrolo pyrrole pigments, benzimidazolone pigment, phthalocyanine color, indigo pigment, perylene ketone (perynone) pigment, perylene dye, phthalein ketone pigment, triazine dioxin pigment, quinacridone pigment, isoindolinone pigment and metal complex pigment, and as yellow iron oxide, red iron oxide, carbon black and the titanium dioxide of inorganic pigment.In case of necessity, except that above coloring pigment, can also use a kind of extender pigment for example talcum, calcium carbonate, blanc fixe and silica together.
This colourful transparent coating in the scope of not damaging its transparency, can contain additive for example modifier, ultra-violet absorber, even paint, dispersant and defoamer.
The dried film thickness that this colourful transparent is filmed better is 10～80 μ m, exceeds at this dried film thickness under the situation of this scope, and this outward appearance of filming may be not enough.The dried film thickness that this colourful transparent is filmed is 20～50 μ m better.Contain in the formation method that glittering material films of the present invention, the glittering coating film of chromatic colour height metal outward appearance can be filmed and obtains by form at least one deck colourful transparent on this flash of light bottom coating, because the light of filming through this colourful transparent is reflected by this flash of light bottom coating, and this reverberation has amplified this flash of light outward appearance.
The example that forms the situation of 2 layers or more multi-layered transparent coating comprises: form a colourful transparent and film and further form the method that a clear varnish is filmed on this flash of light bottom coating, with on this flash of light bottom coating, form a clear varnish and film and further form the method that a colourful transparent is filmed, these can suitably be selected because of purpose is different.
Embodiment
The present invention describes in more detail with reference to following examples, but the present invention is not interpreted as and is limited.
The preparation of Production Example 1 silver colloidal solution
12g is placed a 2L Kolben as the Disperbyk 190 (manufacturing of BYK chemical company) and the 420.5g ion exchange water of polymer pigment dispersant.This Kolben is placed water-bath, and its content is 50 ℃ of stirrings, until Disperbyk 190 dissolvings.Under agitation to wherein adding the 100g silver nitrate that is dissolved in the 420.5g ion exchange water, this content further stirred 10 minutes at 70 ℃.To wherein adding the 262g dimethylamino-ethanol.The rapid blackening of the color of this liquid contents is brought up to 76 ℃ with the temperature of this liquid contents.Allow this liquid contents leave standstill, this liquid contents provides a kind of luteotestaceous silver colloid aqueous solution this temperature continuous stirring 2 hours when this fluid temperature drops to 70 ℃.Resulting reaction solution is transferred in the 1L plastic bottle, and it was left standstill 18 hours in one 60 ℃ thermostatic chamber.By connect a kind of ultrafiltration module (" AHP1010 ", by molecular weight 50,000, several 400 of filter membrane, company of Asahi Chemical Industry makes), magnetic drive pump and bottom with silicone rubber tube the 3L stainless steel cup of pipe connector is arranged, make a ultrafiltration system.The reaction solution that left standstill 18 hours in 60 ℃ of thermostatic chambers is poured in the stainless steel cup,, started pump and carry out ultrafiltration after wherein adding the 2L ion exchange water.After about 40 minutes of experience, when the filtrate quantity of discharging from ultrafiltration module reaches 2L, 2L ethanol is added in this stainless steel cup.After this electrical conductivity that has confirmed this filtrate is 300 μ S/cm or following, this reaction solution is concentrated reach 500mL until this solution.Subsequently, with 500mL stainless steel cup, a ultrafiltration module (" AHP0013 " is by molecular weight 50,000, several 100 of filter membrane, Asahi Chemical Industry's corporate system), a tubular pump and an aspirator that contains this solution, make another ultrafiltration system.The solution of preparation is like this placed this stainless steel cup, concentrate to improve this solid concentration.When the quantity of this solution reaches 100mL, tubular pump is stopped stopping concentrating operation, be 30% silver colloid ethanolic solution thereby obtain a kind of solids content.The average particle diameter of silver colloid is 27nm in this solution.Mensuration with " TG-DTA " (Seiko instrument company system) shows that for 93 (quality) % of initial charge, the content of silver is 96 (quality) % in this solids content.
The preparation of Production Example 2 gold colloid solution
With with Production Example 1 in identical mode, obtaining a kind of solids content is the gold colloid ethanolic solution of 20 (quality) %, different is to use the full acid substitution silver nitrate of chlorine.The average particle diameter of this GOLD FROM PLATING SOLUTION colloid is 18nm.Mensuration with " TG-DTA " shows that for 70 (quality) % of initial charge, the content of gold is 90 (quality) % in this solids content.
Production Example 3 is filmed and is formed synthesizing with resin
[synthesizing of the acrylic resin of phosphorous acidic group]
At an outfit agitator, add 40 mass parts dihydroxypropane single-ethers among the Kolben of thermostat and condenser pipe, dripped 100 mass parts mixed monomer solutions-contain, 8.86 mass parts styrene at 115 ℃ with 3 hour time, 8.27 mass parts EHA, 15.00 mass parts lauryl methacrylate, 34.80 mass parts 2-hydroxyethyl methacrylate, 3.07 mass parts methacrylic acid, with 30.00 mass parts acid phosphorus acyloxy six (oxygen propylidene) monomethacrylates (JAMP-100N, the strong chemical company in city system)-and 43 mass parts initiator solutions-containing 3.0 mass parts to cross the sad tert-butyl ester (Kayaester O) and 40 mass parts dihydroxypropane single-ethers, continuous stirring is 30 minutes subsequently.Then, dripped 20.3 mass parts initiator solutions-contain 0.3 mass parts to cross the sad tert-butyl ester (Kayaester O) and 20 mass parts dihydroxypropane single-ethers with 1 hour time, further stirred subsequently 1.5 hours.The acid number of the phosphorous acidic group acrylic resin that obtains like this is that the acid number of 106mgKOH/g, phosphate is that 86mgKOH/g, hydroxyl value are 150, number-average molecular weight is 3,800, non-volatile 49 (quality) % that is divided into.
Production Example 4 contains the synthetic of glittering material primer
Colloidal solution (solids content 1.5 mass parts) 3 mass parts that Production Example 1 is obtained obtain becoming to be coated with the mixing of film resin (solids content 0.15 mass parts) 0.31 mass parts with Production Example 2.This mixture (contains butyl acetate, propylene glycol monomethyl ether and butyl Cellosolve with 47 mass parts organic solvents, its mass ratio is 5/4/1) dilution, make viscosity be suitable for coating (20 ℃ of 13 seconds/#4 Ford cup), thereby obtain a kind of primer that contains glittering material.Solids content when this primer that contains glittering material is coated with is 2 (quality) %.
The painted mensuration of the silver colloid plasmid gene group preparation and the assay method thereof of filming
Add silver colloidal solution 1.56 mass parts (making that tenor is 1 (quality) % for the resin solid content of this varnish paint) that Production Example 1 obtains to 100 mass parts varnish paint MAC O-1810 Clear (trade names, Nippon company makes, solids content 45 (quality) %) in, prepares a kind of yellow varnish paint.This varnish paint is coated on the glass plate with blade coating cutter (12 Mill),, provides the painted mensuration of a kind of silver colloid plasmid gene group with filming 140 ℃ of bakings 20 minutes.This is filmed and measures resulting value (L with a colour difference meter (CR-200, Minolta corporate system) *a *b *) be converted into the Munsell color system, obtain the painted form and aspect of plasmid gene group (3.8Y).
The painted mensuration of the gold colloid plasmid gene group preparation and the assay method thereof of filming
Add gold colloid solution 2.5 mass parts (making that tenor is 1 (quality) % for the resin solid content of this varnish paint) that Production Example 2 obtains to 100 mass parts varnish paint MAC O-1810 Clear (trade names, Nippon Paint company makes, among solids content 45 (quality) %, prepare a kind of red varnish coating.This coating is coated on the glass plate with blade coating cutter (12 Mill), 140 ℃ of bakings 20 minutes, provides the painted mensuration of a kind of gold colloid plasmid gene group with filming.This is filmed and measures resulting value (L with a colour difference meter (CR-200, Minolta corporate system) *a *b *) be converted into the Munsell color system, obtain the painted form and aspect of plasmid gene group (2.4R).
Embodiment 1～8 and comparative example 1～5 (formation of multilayer film)
The surface of having carried out the aluminum dipping form cast panel of zirconium coating JIS AC4C material that handle, that be of a size of thick 10mm, long 10cm, wide 15cm cut iridescent surfaces of formation, to reach build be 100 μ m to a kind of acrylic resin epoxide powder coating of electrostatic applications Biryusia HB2000 Clear (manufacturing of Nippon company) thereon, 160 ℃ of bakings 30 minutes, form a kind of bottom coating then.
To have the priming paint putty coating of various form and aspect respectively to be sprayed on the resulting bottom coating, reaching dried film thickness is 30 μ m, leaves standstill then 5 minutes, subsequently 140 ℃ of bakings 30 minutes, forms priming paint putty and films.
As the bottom coating that contains glittering material, the glittering material primer that contains that Production Example 4 is obtained is sprayed on this priming paint putty films, and reaching dried film thickness is 0.1 μ m, leaves standstill then 10 minutes, 140 ℃ of bakings 30 minutes, form a kind of bottom coating that contains glittering material subsequently.
Film as varnish, with a kind of acrylic compounds melamine solvent based coating (Super Lacq 5000AW10 Clear, the Nippon corporate system) spraying thereon, reach dried film thickness and be 30 μ m, then leave standstill 10 minutes, subsequently 140 ℃ of bakings 30 minutes, form a kind of varnish and film.Like this, just, obtain a kind of multilayer film.
The painted mensuration of plasmid gene group that obtains in order to last method with film (containing the glittering material bottom coating), priming paint putty is filmed and multilayer film is measured as follows:
Form and aspect
Form and aspect are to measure with a colour difference meter (CR-200, Minolta corporate system).The painted mensuration of plasmid gene group is as L with the form and aspect of filming and priming paint putty is filmed *a *b *Measure, and be converted into the Munsell color system.The form and aspect of this multilayer film are as a value and b pH-value determination pH.
Gloss
The gloss of this multilayer film is fixed with the HandyGlossmeter PG-1M pool that NDK company makes as 60 ° of gloss.
Visual assessment
Design performance to this multilayer film is carried out visual assessment.The form and aspect of this multilayer film and gloss are with 5 grades of assessments, and silver color that this noble metal is intrinsic or gold are the 5th grade.
The painted mensuration of plasmid gene group is listed in the following table 1 with the measurement result of filming and priming paint putty is filmed.The measurement result of this multilayer film is listed in the following table 2.
Figure A20081013017000231
Table 2
Figure A20081013017000241
60 ° of gloss of the multilayer film of embodiment 1～8, use under the situation of gold colloid be 200 or more than, under the situation of using silver colloid be 400 or more than, demonstrate excellent gloss.These are filmed and can not cause that design performance worsens owing to form and aspect change.On the other hand, in comparative example 1～5, find that form and aspect change or gloss reduces, and design performance worsens.
In general, the gloss number that can reach with the metal coating composition that contains the strip glittering material be 150 or below, and be about 200 with the gloss number that minute surface can reach.The surface of metal coating has 400 or above gloss number.
Therefore, the invention provides a kind of coating technique that does not usually reach as yet, thereby the outward appearance that demonstrates the intrinsic gloss of noble metal can obtain by coating.The metallic luster of multilayer film provided by the present invention is equivalent to the surface of metal coating, but multilayer film formation method of the present invention does not need the processing of needed heavy metal-containing waste water in the metal-plated embrane method, causes remarkable circlet border load.
According to the present invention, provide a kind of formation method of multilayer film of the metallic luster with design performance excellence.

Claims (3)

1. multilayer film formation method is included in and wants to form in order on the substrates coated bottom coating and varnish that a priming paint putty is filmed, one contains glittering material and film,
The colloidal particles that the primer that contains glittering material that is used to form this bottom coating that contains glittering material contains noble metal and/or metal become to be coated with film resin with a kind of, and
This priming paint putty films to be rotated counterclockwise on hue circle on Munsell 100 hue circles that turn clockwise with 0～+ 50 expression with 0～-50 expression to be had+form and aspect in 35～+ 50 and-35～-50 scopes; wherein these painted form and aspect of plasmid gene group that contain the colloidal particles of noble metal and/or metal are 0 on this hue circle; and the briliancy on the Munsell color system be 9 or below, or this priming paint putty a kind of briliancy on the Munsell color system of filming is 4 or following achromatic colour.
2. the described multilayer film of claim 1 formation method, wherein this one-tenth is coated with film resin and contains the phosphorous acidic group acrylic resin of 30～100 quality %, the acid number of its phosphate is 70～150mgKOH/g, the total acid number that comprises the acid number of other acidic group is 70～200mg KOH/g, hydroxyl value is 50～220mg KOH/g, and number-average molecular weight is 2000～8000.
3. multilayer film, it forms with claim 1 or 2 described multilayer film formation methods.
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